Substituted 1,4-diamino-2-butene stabilizers and stabilized compositions

ABSTRACT

N,N,N&#39;,N&#39;-Tetrasubstituted 1,4-diamino-2-butenes where the substituents are alkyl, cycloalkyl, aralkyl, aryl or mixtures thereof provide effective antioxidant protection to lubricants and/or synthetic polymers.

This is a divisional of application Ser. No. 08/146,377, filed on Nov.1, 1993, now U.S. Patent No. 5,391,808, issued on Feb. 21, 1995, whichis a divisional of application Ser. No. 07/701,268, filed on May 16,1991, now U.S. Pat. No. 5,283,367, issued on Feb. 1, 1994, which is acontinuation-in-part of application Ser. No. 07/400,649, filed on Aug.30, 1989, now abandoned.

N,N,N',N'-Tetrasubstituted 1,4-diamino-2-butenes where the substituentsare alkyl, cycloalkyl, aralkyl, aryl or mixtures thereof provideeffective antioxidant protection to lubricants and/or syntheticpolymers.

BACKGROUND OF THE INVENTION

The instant substituted 1,4-diamino-2-butene compounds fall into threegeneral groups depending on the various substituents on the two N-atoms.

When said substituents are alkyl, compounds having at least one loweralkyl, preferably two lower alkyl groups, on each N-atom are known.Lower alkyl includes methyl, ethyl, propyl butyl and amyl. Typical isN,N,N',N'-tetramethyl-2-butene-1,4-diamine. The use of such lower alkylcompounds as stabilizers is not disclosed. The instant alkylsubstituents are higher alkyls such as octyl, decyl, octadecyl and thelike.

When said substituents are aralkyl, the hydrochloride salt of such thetetrabenzyl compound has a GAS number (5443-70-9), but no otherpublished reference is known for said material nor is there any knownutility for said compound. The other tetra-aralkyl compounds arebelieved to be novel materials. The stabilized compositions where thestabilizers are the instant compounds having one or more aralkylsubstituents are not disclosed in the prior art.

When said substituents are aryl, British Patent No. 1,438,482generically describes lubricant compositions containing substituted arylmines of the formula R--X where R is a secondary amine residuecontaining two aromatic groups attached to nitrogen such as (Ar)₂ N--.This reference also generically describes compounds of the formulaR--Y--R where Y is inter alia --CH₂ CH═CHCH₂ --. The only such compoundsspecifically disclosed by the British reference are those where R is analkylated phenothiazine moiety. The closest compound of this referenceis 1,4-but-2-ene-bis(3,7-dioctylphenothiazine).

British Patent No. 1,438,482 does not disclose or suggest that thecompounds described therein can provide effective antioxidant protectionto synthetic polymer compositions.

OBJECTS OF THE INVENTION

On object of this invention is to provide new N,N,N',N'-tetrasubstituted1,4-diamino-2-butene compounds which are useful stabilizers for varioussubstrates.

Another object of this invention is to provide synthetic polymercompositions stabilized by incorporating therein an effectivestabilizing amount of an instant compound.

Still another object of the invention is to provide a lubricantcomposition stabilized by incorporating therein an effective stabilizingamount of an instant compound.

DETAILED DISCLOSURE

The instant invention pertains to a composition stabilized against thedeleterious effects of heat or oxygen which comprises

(a) a synthetic polymer or a lubricant, and

(b) an effective stabilizing mount of a compound of formula I, II or III##STR1## wherein R₁, R₂, R₃ and R₄ are independently a linear orbranched alkyl of 8 to 30 carbon atoms; alkyl of 1 to 20 carbon atomssubstituted with cycloalkyl of 5 to 12 carbon atoms; or alkyl of 1 to 20carbon atoms terminated with --OR₅, --NR₆ R₇,--SR₈, --COOR₉ or --CONR₁₀R₁₁, where R₅, R₆, R₇, R₈ and R₉ are independently alkyl of 1 to 20carbon atoms or alkenyl of 3 to 18 carbon atoms, and R₁₀ and R₁₁ areindependently hydrogen or the same meaning as Rs; or alkyl of 3 to 18carbon atoms interrupted by one or more --O--, --S--, --SO--, --SO₂ --,--CO--, --COO--, --OCO--, --CONR₁₂ --, --NR₁₂ CO-- or --NR₁₃ -- whereR12 and R13 have the same meaning as R₁₀ ; or R₁, R₂, R₃ and R₄ areindependently cycloalkyl of 5 to 12 carbon atoms; or alkenyl of 3 to 20carbon atoms;

E₁ is aralkyl of 7 to 15 carbon atoms or said aralkyl substituted on thearyl ring by one to three groups selected from alkyl of 1 to 12 carbonatoms, --CN, --NO₂, halogen, --OR₅, --NR₆ R₇, --SR₈, --COOR₉ or --CONR₁₀R₁₁, where R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are as defined above,

E₂, E₃ and E₄ are independently a linear or branched alkyl of 1 to 30carbon atoms; alkyl of 1 to 20 carbon atoms substituted with cycloalkylof 5 to 12 carbon atoms; or alkyl of 1 to 20 carbon atoms terminatedwith --CN, --OR₅, --NR₆ R₇, --SR₈, --COOR₉ or --CONR₁₀ R₁₁, where R₅,R₆, R₇, R₈ and R₉ are independently alkyl of 1 to 20 carbon atoms oralkenyl of 3 to 18 carbon atoms, and R₁₀ and R₁₁ are independentlyhydrogen or the same meaning as R₅ ; or alkyl of 3 to 18 carbon atomsinterrupted by one or more --O--, --S--, --SO--, --SO₂ --, --CO--,--COO--, --OCO--, --CONR₁₂ --, -- NR₁₂ CO-- or --NR₁₃ -- where R₁₂ andR₁₃ have the same meaning as R₁₀ ; or E₂, E₃ and E₄ are independentlycycloalkyl of 5 to 12 carbon atoms, alkenyl of 3 to 20 carbon atoms,aralkyl of 7 to 15 carbon atoms or said aralkyl substituted on the arylring by one to three groups selected from alkyl of 1 to 12 carbon atoms,--CN, --NO₂, halogen, --OR₅, --NR₆ R₇, --SR₈, --COOR₉ or --CONR₁₀ R₁₁,where R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are as defined above, or aryl of 6to 10 carbon atoms or said aryl substituted by one to three substituentsselected from the group consisting of alkyl of 1 to 20 carbon atoms,cycloalkyl of 5 to 12 carbon atoms and aralkyl of 7 to 15 carbon atoms,and

T₁, T₂, T₃ and T₄ are independently aryl of 6 to 10 carbon atoms or saidaryl substituted by one to three substituents selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12carbon atoms and aralkyl of 7 to 15 carbon atoms.

Preferably R₁, R₂, R₃ and R₄ are independently cycloalkyl of 5 or 6carbon atoms, a linear or branched alkyl of 8 to 20 carbon atoms oralkyl of 1 to 4 carbon atoms substituted with cycloalkyl of 5 or 6carbon atoms.

Most preferably R₁, R₂, R₃ and R₄ are the same and are alkyl of 8 to 18carbon atoms, cyclohexyl or cyclohexylmethyl.

Preferably E₁ is benzyl, benzyl substituted on the phenyl ring by alkylof 1 to 8 carbon atoms, α-methylbenzyl or 1-naphthylmethyl.

Most preferably E₁ is benzyl or 1-naphthylmethyl.

Preferably E₂, E₃ and E₄ are independently alkyl of 1 to 20 carbonatoms, benzyl, benzyl substituted on the phenyl ring by alkyl of 1 to 8carbon atoms or by methoxycarbonyl, phenyl, 1-naphthyl or said phenyl orsaid 1-naphthyl substituted by alkyl of 1 to 8 carbon atoms;cyclohexylmethyl or 2-cyanoethyl.

Most preferably E₃ has the same meaning as E₁ and is benzyl or1-naphthylmethyl; and E₂ and E₄ are alkyl of 1 to 20 carbon atoms,benzyl or 1-naphthylmethyl.

Preferably T₁, T₂, T₃ and T₄ are independently phenyl, 1-naphthyl orsaid phenyl or said 1-naphthyl substituted by alkyl of 1 to 8 carbonatoms.

Most preferably T₁ and T₃ are phenyl, and T₂ and T₄ are phenyl or1-naphthyl. Especially preferably, T₁, T₂, T₃ and T₄ are each phenyl.

The compounds of formula I and formula II are conveniently prepared byreacting an appropriate secondary amine with 2-butene-1,4-diol diacetatein the presence of a catalyst such astetrakis(triphenylphosphine)palladium(0) in an organic solvent such astetrahydrofuran.

The compounds of formula III are conveniently prepared by the reactionof the appropriate secondary diarylamine with 1,4-dibromobut-2-ene inthe presence of an aqueous mixture of potassium iodide, a phase transfercatalyst and alkali.

The starting materials for making the instant compounds are largelyitems of commerce.

When any of the aforementioned groups of R₁ to T₄ are alkyl, they are,for example, methyl, ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl,isoamyl, tert-amyl, n-hexyl, 2-ethylhexyl, isooctyl, n-octyl,tert-octyl, nonyl, decyl undecyl, lauryl, tridecyl, tetradecyl,hexadecyl, heptadecyl, octadecyl, eicosyl, tricontyl and branchedisomers thereof.

Cycloalkyl of 5 to 12 carbon atoms includes, for example, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl.

Phenylalkyl of 7 to 9 carbon atoms includes, for example, benzyl,phenethyl, α-methylbenzyl and α,α-dimethylbenzyl.

Aryl of 6 to 10 carbon atoms includes, for example, phenyl, 1-naphthyland 2-naphthyl.

Aryl or phenylalkyl substituted by alkyl is, for example, tolyl, xylyl,ethylphenyl, 4-methylbenzyl, tert-butylphenyl, tert-octylphenyl,tert-dodecylphenyl, nonylnaphthyl or tert-octylnaphthyl.

The compositions where component (a) is a synthetic polymer areespecially a part of this invention, most particularly when thesynthetic polymer is a polyolefin such as polypropylene or is anelastomer such as dynamically crosslinked polypropylene/nitrile rubber.

The instant compounds are effective stabilizers for synthetic polymerssubject to the deleterious effects of heat and/or oxygen especiallyduring processing at elevated temperatures.

Still another part of this invention, especially where the substituentgroups on the N-atoms are aryl or phenylalkyl, are compositions wherecomponent (a) is an industrial lubricant such as lubricating oils,turbine oils, transformer oils, transmission fluids, glass-annealingoils, greases, steam turbine oils, gasoline engine oils, diesel engineoils, jet engine oils, metal working fluids and the like. They are alsoeffective in stabilizing waxes, heating oil, bunker and residual oils,asphalt, gasoline and jet engine fuel.

Still another aspect of the instant invention are the novel compounds offormula I or formula II ##STR2## wherein R₁, R₂, R₃ and R₄ ; and E₁, E₂,E₃ and E₄ are as defined above; with the proviso that E₁, E₂, E₃ and E₄are not all benzyl at the same time.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polyethylene(which optionally can be crosslinked), polypropylene, polyisobutylene,polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene, aswell as polymers of cycloolefins, for instance of cyclopentene ornorbornene.

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene.

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, such as, for example, ethylene/propylene,propylene/butene-1, propylene/isobutylene, ethylene/butene-1,propylene/butadiene, isobutylene/isoprene, ethylene/alkyl acrylates,ethylene/alkyl methacrylates, ethylene/vinyl acetate or ethylene/acrylicacid copolymers and their salts (ionomers) and terpolymers of ethylenewith propylene and a diene, such as hexadiene, dicyclopentadiene orethylidene-norbomene.

4. Polystyrene, poly-(p-methylstyrene).

5. Copolymers of styrene or methylstyrene with dienes or acrylicderivatives, such as, for example, styrene/butadiene,styrene/acrylonitrile, styrene/ethyl methacrylate,styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength from styrene copolymers and anotherpolymer, such as, for example, from a polyacrylate, a diene polymer oran ethylene/propylene/diene terpolymer; and block polymers of styrene,such as, for example, styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene, such as, for example, styrene onpolybutadiene, styrene and acrylonitrile on polybutadiene, styrene andalkyl acrylates or methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyacrylates or polymethacrylates, styrene andacrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 5), for instance the copolymermixtures known as ABS-, MBS-, ASA- or AES-polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrinhomo- and copolymers, polymers from halogen-containing vinyl compounds,as for example, polyvinylchloride, polyvinylidene chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof, as forexample, vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate, vinylidene chloride/vinyl acetate copolymers, or vinylfluoride/vinyl ether copolymers.

8. Polymers which are derived from α,β-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates, polyacrylamide andpolyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other orwith other unsaturated monomers, such as, for instance,acrylonitrile/butadiene, acrylonitrile/alkyl acrylate,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halogenidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, oracyl derivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinylbutyral, polyallyl phthalate or polyallyl-melamine.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as comonomer.

13. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with polystyrene.

14. Polyurethanes which are derived from polyethers, polyesters orpolybutadienes with terminal hydroxyl groups on the one side andaliphatic or aromatic polyisocyanates on the other side, as well asprecursors thereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,polyamide 6/10, polyamide 11, polyamide 12,poly-2,4,4-trimethylhexamethylene terephthalamide, poly-p-phenyleneterephthalamide or poly-m-phenylene isophthalamide, as well ascopolymers thereof with polyethers, such as for instance withpolyethylene glycol, polypropylene glycol or polytetramethylene glycols.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diolsand/or from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylol-cyclohexane terephthalate,poly-[2,2-(4-hydroxyphenyl)-propane] terephthalate andpolyhydroxybenzoates as well as block-copolyether-esters derived frompolyethers having hydroxyl end groups.

18. Polycarbonates.

19. Polysulfones, polyethersulfones and polyetherketones.

20. Crosslinked polymers which are derived from aldehydes on the onehand and phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

23. Thermosetting acrylic resins, derived from substituted acrylicesters, such as epoxy-acrylates, urethane-acrylates or polyesteracrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture withmelamine resins, urea resins, polyisocyanates or epoxide resins ascrosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, forexample from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatin and derivativesthereof which are chemically modified in a polymer homologous manner,such as cellulose acetates, cellulose propionates and cellulosebutyrates, or the cellulose ethers, such as methyl cellulose.

27. Mixtures of polymers as mentioned above, for example PP/EPDM,Polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS.

28. Naturally occuring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, which materials may be used as plasticizers forpolymers or as textile spinning oils, as well as aqueous emulsions ofsuch materials.

29. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

30. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

31. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

32. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

33. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE-4103 (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.5 to about 2%, and especially 0.1 toabout 1%.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain from about 0.01 to about 5%, preferably from about 0.025 toabout 2%, and especially from about 0.1 to about 1% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

1. Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert.butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroquinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2'-thio-bis-(6-tert-butyl-4-methylphenol)

2,2'-thio-bis-(4-octylphenol)

4,4'-thio-bis-(6-tert-butyl-3-methylphenol)

4,4'-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2'-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2'-methylene-bis-(6-nonyl-4-methylphenol)

2,2'-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2'-methylene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4'-methylene-bis-(2,6-di-tert-butylphenol)

4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl-butane

2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl--N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol       diethylene glycol                                              octadecanol    triethylene glycol                                             1,6-hexanediol pentaerythritol                                                neopentyl glycol                                                                             tris-hydroxyethyl isocyanurate                                 thiodiethylene glycol                                                                        di-hydroxyethyl oxalic acid diamide                            ______________________________________                                    

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

    ______________________________________                                        methanol       diethylene glycol                                              octadecanol    triethylene glycol                                             1,6-hexanediol pentaerythritol                                                neopentyl glycol                                                                             tris-hydroxyethyl isocyanurate                                 thiodiethylene glycol                                                                        di-hydroxyethyl oxalic acid diamide                            ______________________________________                                    

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

1.10 Diarylamines, for example, diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,4,4'-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and 2,4,4-trimethylpentene, reaction product ofdiphenylamine and 2,4,4-trimethylpentene, reaction product ofN-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.

2. UV absorbers and light stabilizers

2.1.2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3',5'-di-tert-butyl-, 5'-tert-butyl-, 5'-(1,1,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-,3'-sec-butyl-5'-tert-butyl-, 4'-octoxy, 3',5'-di-tert-amyl-, 3',5'-bis-(α,α-dimethylbenzyl),3'-tert-butyl-5'-(2-(omega-hydroxy-octa-(ethylencoxy)carbonyl-ethyl)-,3'-dodecyl-5'-methyl-, and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-,and dodecylated-5'-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2',4'-trihydroxy-and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl)sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N'-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate.

2.7. Oxalic acid diamides, for example, 4,4'-di-octyloxy-oxanilide,2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide,2-ethoxy-2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy-as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino, 1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearylsorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4'-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

The phenolic antioxidant of particular interest is selected from thegroup consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2'-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2'-ethylidene-bis(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane,polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazineand 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4'-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-2,2,6,6-tetramethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane, mixed[2,2,6,6-tetramethylpiperidin-4-yl/lβ,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate,mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate,octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4'-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one) andbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperdine andsuccinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N',N",N"'-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazine-2-yl]1,10-diamino-4,7-diazadecaneor bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate.

The lubricant of component (a) is particularly a lubricating oil orgrease wherein the base medium is a hydrocarbon or synthetic lubricant.The preferred base fluids of this invention include the hydrocarbonmineral oils, olefin fluids, polyolefin fluids, polyether fluids,polyacetals, alkylene oxide polymers, silicone-base fluids and esterfluids. The esters of dicarboxylic acids and monohydric alcohols and thetrimethylolpropane and pentaerythritol esters of monocarboxylic acidsare particularly of interest. Suitable diesters include the esters ofoxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaicand sebacic acids, cyclohexane dicarboxylic acid, phthalic acid,terephthalic acid and the like; and alcohols having 1 to 20 carbonatoms. A commonly used diester is di(2-ethylhexyl) sebacate.

The acids used in forming the trimethylolpropane and pentaerythritolesters include those containing 1 to 30 carbon atoms having straight orbranched chain aliphatic, cycloaliphatic, aromatic or alkylated aromaticstructures. Mixtures of one or more of such acids may also be used inthe preparation of these tri-and tetra-esters. Typical carboxylic acidsinclude, acetic, propionic, butyric, valeric, isovaleric, caproic,caprylic, pelargonic, capric, isodecanoic, lauric, benzoic,nonylbenzoic, dodecylbenzoic, naphthoic, cyclohexanoic and the like. Theacids most particularly preferred are pelargonic and commeric valericacid which contains both n-valeric and isovaleric acids.

The most preferred ester used in this invention is an ester preparedfrom pentaerythritol, pelargonic, n-valeric and isovaleric acids.

The instant compounds are sufficiently soluble in lubricants to affordthe desired antioxidant stabilizing effects. Suitable concentrationsrange from about 0.001% to about 10% by weight based on the totallubricant composition. Preferably the effective stabilizing amount ofthe instant compounds is from about 0.1% to about 5% by weight of thetotal lubricant composition.

The lubricant composition of the instant invention find a wide varietyof end uses including engine oils, such as aviation engine oils,automotive engine oils, diesel engine oils, railroad diesel oils, truckdiesel oils and the like.

The lubricating oil may be a mineral oil, a synthetic oil or any mixtureof such oils. Mineral oils are preferred and examples of these includeparaffinic hydrocarbon oils e.g. a mineral oil having a viscosity of 46mm² /s at 40° C.; "150 Solvent Neutral" a solvent refined neutralmineral oil having a viscosity of 32 mm² /s at 40° C.; and "solventbright-stocks", a high boiling residue from the process of refiningmineral oil, and having a viscosity of 46 mm² /s at 40° C.

Synthetic lubricating oils which may be present may be synthetichydrocarbons such as polybutenes, alkyl benzenes and poly-alpha olefinsas well as simple di-, tri- and tert-esters, complex esters andpolyesters derived from carboxylic acid esters of formula: G₁-OCC-alkylene-COOG₂ wherein "alkylene" denotes an alkylene residuehaving from 2 to 14 carbon atoms and G₁ and G₂ are the same or differentand each is an alkyl group having from 6 to 18 carbon atoms. Tri-esterswhich are of use as lubricating oil base stocks are those derived fromtrimethylolpropane and C₆ -C₁₈ mono-carboxylic acids or mixturesthereof, whereas suitable tetra-esters include those derived frompentaerythritol and a C₆ -C₁₈ mono-carboxylic acid or mixtures thereof.

Complex esters suitable for use as components of the composition of thepresent invention are those derived from monobasic acids, dibasic acidsand polyhydric alcohols, for instance the complex ester derived fromtrimethylol propane, caprylic acid and sebacic acid.

Suitable polyesters are those derived from any aliphatic dicarboxylicacid having from 4 to 14 carbon atoms and at least one aliphaticdihydric alcohol having from 3 to 12 carbon atoms, e.g. those derivedfrom azelaic acid or sebacic acid and 2,2,4-trimethylhexane-1,6-diol.

Other lubricating oils are those known to the art-skilled and describede.g. in Schewe-Kobek, "Schmiermittel-Taschenbuch", (Huethig Verlag,Heidelberg 1974), and in D. Klamann, "Schmierstoff und verwandteProdukte", (Verlag Chemic, Weinheim 1982).

The lubricating oils applicational media can also contain otheradditives which may be added to improve the basic properties oflubricants e.g. metal passivators, viscosity-index improvers, pour-pointdepressants, dispersing agents, detergents, additional rust inhibitors,extreme pressure additives, anti-wear additives and antioxidants.

Examples of phenolic antioxidants

1. Alkylated Monophenols 2,6-Di-tert-butyl-4-methylphenol,2,6-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethyl-phenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol,2-(β-methylcyclohexyl)-4,6-dimethylphenol,2,6-di-octa-decyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, o-tert-butylphenol.

2. Alkylated Hydroquinones 2,6-Di-tert-butyl-4-methoxyphenol,2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone,2,6-diphenyl-4-octa-decyloxyphenol.

3. Hydroxylated Thiodiphenylethers 2,2'-Thio-bis-(6-tert-butyl-4-methylphenol), 2,2'-thio-bis-(4-octyl-phenyl),4,4'-thio-bis-(6-tert-butyl-3-methylphenol),4,4'-thio-bis-(6-tert-butyl-2-methylphenol).

4. Alkylidene-Bisphenols2,2'-Methylene-bis-(6-tert-butyl-4-methylphenol),2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol),2,2'-methylene-bis-(4-methyl-6-(α-methyl-cyclohexyl)-phenol),2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol),2,2'-methylene-bis-(6-nonyl-4-methylphenol),2,2'-methylene-bis-(4,6-di-tert-butylphenol),2,2'-ethylidene-bis-(4,6-di-tert-butylphenol),2,2'-ethylidene-bis-(6-tert-butyl-4- or -5-isobutylphenol),2,2'-methylene-bis-(6-(α-methylbenzyl-4-nonylphenol),2,2'-methylene-bis-(6-(α,α-di-methylbenzyl)-4-nonylphenol),4,4'-methylene-bis-(2,6-di-tert-butyl-phenol),4,4'-methylene-bis-(6-tert-butyl-2-methylphenol),1,1-bis-(5-tert-butyl-4-hydroxy-2-methyl-phenol)-butane,2,6-di-(3-tert-butyl-5-methyl-2-hydroxy-benzyl)-4-methyl-phenol,1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecyl)-mercaptobutane,ethyleneglycol-bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate],bis-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene,bis-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-methyl-phenyl]-terephthalate.

5. Benzyl Compounds1,3,5-Tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene,bis(3,5-di-tert-butyl-4-hydroxybenzyl)-sulfide,3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid-isooctylester,bis-(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl)dithiolterephthalate,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate,1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate,3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-dioctadecylester,3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-monoethylester,calcium-salt.

6. Acrylaminophenols 4-Hydroxy-lauric acid anilide, 4-hydroxy-stearicacid anilide,2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine,N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamic acid octyl ester.

7. Esters of β-(3,5-Di-tert-butyl-4-hydroxyphenol)-propionic acid withmono- or polyhydric alcohols, for example with methanol,diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexane-diol,pentaerythritol, neopentylglycol, tris-hydroxyethyl-isocyanurate,thiodiethyleneglycol, bis-hydroxyethyl-oxalic acid diamide.

8. Esters of β(5-tert-butyl-4-hydroxy-3-methylphenyl)-priopionic acidwith mono-or polyhydric alcohols, for example with methanol,diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexane-diol,pentaerythritol, neopentylglycol, tris-hydroxyethyl-isocyanurate,thiodiethyleneglycol, di-hydroxyethyl-oxalic acid diamide.

9. Amides of β-(3,5-Di-tert-butyl-4-hydroxyphenyl)-propionic acid forexampleN,N'-Bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylene-diamine,N,N'-bis-(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-trimethylene-diamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine.

Examples of amine antioxidants: N,N'-Di-isopropyl-p-phenylenediamine,N,N'-di-sec.-butyl-p-phenylenediamine,N,N'-bis(1,4-dimethyl-pentyl)-p-phenylenediamine,N,N'-bis(1-ethyl-3-methyl-pentyl)-p-phenylenediamine,N,N'-bis(1-methyl-heptyl)-p-phenylenediamine,N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine,N,N'-di-(naphthyl-2-)-p-phenylenediamine,N-isopropyl--N'-phenyl-p-phenylenediamine,N-(1,3-dimethyl-butyl)-N'-phenyl-p-phenylenediamine,N-(1-methyl-heptyl)--N'-phenyl-p-phenylene-diamine,N-cyclohexyl-N'-phenyl-p-phenylenediamine,4-(p-toluene-sulfonamido)-diphenylamine,N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, di-phenylamine,N-allyldiphenylamine, 4-isopropoxy-diphenylamine,N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylateddiphenylamine, e.g. p,p'-di-tert-octyldiphenylamine,4-n-butylaminophenol, 4-butyrylamino-phenol, 4-nonanoylamino-phenol,4-dodecanoyl-amino-phenol, 4-octadecanoyl-amino-phenol,di-(4-methoxy-phenyl)-amine,2,6-di-tert-butyl-4-dimethyl-amino-methyl-phenol,2,4'-diamino-diphenylmethane, 4,4'-diamino-diphenyl-methane,N,N,N',N'-tetramethyl-4,4'-diamino-diphenylmethane,1,2-di-(phenyl-amino)ethane, 1,2-di-[2-methyl-phenyl)-amino]-ethane,1,3-di-(phenylamino)-propane, (o-tolyl)-biguanide,di-[4-1',3'-dimethyl-butyl)-phenyl]amine, tert-octylatedN-phenyl-1-naphthylamine, mixture of mono- and dialkylatedtert-butyl-/tert-octyldiphenylamines,2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine,N-allylphenothiazine.

Examples for other antioxidants: Aliphatic or aromatic phosphites,esters of thiodipropionic acid or of thiodiacetic acid, or salts ofdithiocarbamic or dithiophosphoric acid.

Examples of metal passivators, for example for copper, are: Triazoles,benzotriazoles and derivatives thereof, tolutriazole and derivativesthereof, e.g. di(2-ethylhexyl)-aminomethyltolutriazole,2-mercaptobenzothiazole, 5,5'-methylene-bis-benzotriazole,4,5,6,7-tetrahydrobenzo-triazole, salicyclidene-propylene-diamine andsalicyclamino-guanidine and salts thereof, 1,2,4-triazole andN,N'-disubstituted aminomethyl triazoles of formula ##STR3## in which R₈and R₉ are, independently, e.g. alkyl, alkenyl, or hydroxyethyl,obtained by reacting 1,2,4-triazole with formaldehyde and an amine, HNR₈R₉, as disclosed in European Patent Application No. 160620; and theMannich reaction products derived from benzotriazole or tolutriazole,formaldehyde and an amine HNR₈ R₉.

Examples of rust inhibitors are:

a) Organic acids, their esters, metal salts and anhydrides, e.g.N-oleoyl-sarcosine, sorbitan-mono-oleate, lead-naphthenate,alkenyl-succinic acids and-anhydrides, e.g. dodecenyl-succinic acidanhydride, succinic acid partial esters and amines,4-nonyl-phenoxy-acetic acid.

b) Nitrogen-containing compounds, e.g.

I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines andamine-salts of organic and inorganic acids, e.g. oil-solublealkyl-ammonium carboxylates

II. Heterocyclic compounds, e.g. substituted imidazolines andoxazolines.

c) Phosphorus-containing compounds, e.g. amine salts of phosphonic acidor phosphoric acid partial esters, zinc dialkyldithio phosphates.

d) Sulfur-containing compounds, e.g.barium-dinonylnaphthalene-n-sulfonates, calcium petroleum sulfonates.

e) Derivatives of gamma-alkoxypropylamines described in Japanese PatentPublication No. 15783/1973; and

f) Salts having the formula Y--NH₃ --R₁₀ CO₂ -- in which Y is a groupR₁₁ X₁ CH₂ CH(OH)CH₂ in which R₁₀ and R₁₁, independently, are e.g. alkyland X₁ is O, CO₂, NH, N(alkyl), N(alkenyl) or S, these salts beingprepared by mixing an amine Y--NH₂ with an acid R₁₀ CO₂ H, as disclosedin DE-OS 3437 876 (German Offenlegungsschrift).

g) Compounds having the formula

    R.sub.12 --X.sub.2 --CH.sub.2 --CH(OH)--CH.sub.2 NR.sub.13 R.sub.14

in which X₂ is --O--, --S--, --SO₂ --C(O)--O-- or --N(Rd) in which R₁₂is H or C₁ -C₁₂ alkyl, R₁₃ is unsubstituted C₁ -C₄ alkyl or C₂ -C₅ alkylsubstituted by one to three hydroxyl groups, R₁₄ is hydrogen,unsubstituted C₁ -C₄ alkyl or C₂ -C₅ alkyl substituted by one to threehydroxyl groups provided that at least one of R₁₃ and R₁₄ ishydroxy-substituted, and R₁₂ is C₂ -C₂₀ alkyl --CH₂ --CH(OH)--CH₂ NR₁₃R₁₄ or R₁₂ is C₂ -C₁₈ alkenyl, C₂ -C₃ alkynyl or C₅ -C₁₂ cycloalylprovided that, when X₂ is --O-- or --C(O)--O--, R₁₂ is branched C₄ -C₂₀alkyl. These compounds are described in GB Patent Specification2172284A.

h) Compounds having the formula: ##STR4## in which R₁₅, R₁₆, R₁₇ are,independently, hydrogen, C₁ -C₁₅ alkyl, C₅ -C₁₂ cycloalkyl, C₆ -C₁₅ arylor C₇ -C₁₂ aralkyl and R₁₈ and R₁₉, independently, are hydrogen,2-hydroxyethyl or 2-hydroxypropyl, provided that R₁₈ and R₁₉ are notsimultaneously hydrogen and, when R₁₈ and R₁₉ are each --CH₂ CH₂ OH, R₁₅and R₁₆ are not simultaneously hydrogen and R₁₇ is not pentyl. Thesecompounds are described in EP Patent specification 0 252 007.

Examples of viscosity-index improvers are: Polyacrylates,polymethacrylates, vinylpyrrolidone/methacrylate-copolymers,polyvinylpyrrolidones, polybutanes, olefin-copolymers,styrene/-acrylate-copolymers, polyethers.

Examples of pour-point depressants are: Polymethacrylates, alkylatednaphthalene derivatives.

Examples of dispersants/detergents are: Polybutenylsuccinic acid-amidesor imides, polybutenyl-phosphonic acid derivatives, basic magnesium-,calcium-, and bariumsulfonates and -phenolates.

Examples of anti-wear additives and extreme pressure additives are:Sulphur- and/or phosphorus- and/or halogen-containing compounds e.g.sulphurised vegetable oils, zinc dialkyldithiophosphates,tritolylphosphate, chlorinated paraffins, alkyl- and aryldi- andtrisulphides, triphenylphosphorothionate.

The following examples are presented for the purpose of illustrationonly and are not to be construed to limit the nature or scope of theinstant invention in any manner whatsoever.

EXAMPLE 1 N,N,N',N'-Tetradecyl-2-butene-1,4-diamine

A solution of di-n-decylamine (10.9 g, 36.6 mmol) and 2-butene-1,4-dioldiacetate (3.15 g, 18.3 mmol) in tetrahydrofuran (THF) (150 ml) istreated with tetrakis(triphenylphosphine)palladium(0) (1.0 g, 0.9 mmol)and stirred at room temperature overnight. The reaction mixture isconcentrated in vacuo to a oil that is redissolved in THF (500 ml) andtreated with 20% aqueous sodium hydroxide (250 ml). The mixture isstirred for one hour, concentrated, and extracted with ether. The etherextracts are dried and concentrated giving an orange oil which ispurified by medium pressure chromatography (silica gel; 25% ethylacetate in hexanes). The title compound is isolated as 5.8g (49% yield)of a clear oil.

Analysis: Calcd for C₄₄ H₉₀ N₂ : C, 81.6; H, 14.0; N, 4.3. Found: C,81.4; H, 14.2; N, 4.7.

EXAMPLE 2 N,N,N',N'-Tetracyclohexylmethyl-2-butene-1,4-diamine

A solution of dicyclohexylmethylamine (13.3 g, 63.6 mmol) and2-butene-1,4-diol diacetate (5.45 g, 31.8 mmol) in THF (100 ml) istreated with tetrakis(triphenylphosphine)palladium(0) (1.0 g, 0.9 mmol)and stirred at room temperature overnight. The reaction mixture isconcentrated in vacuo to a solid that is redissolved in THF (500 ml) andtreated with 20% aqueous sodium hydroxide (250 ml).The mixture isstirred for one hour, concentrated, and extracted with ether. The etherextracts are dried and concentrated giving an orange solid which ispurified by crystallization from isopropyl alcohol. The title compoundis isolated as a white solid in a yield of 10.7g (71%): mp 72°-73° C.

Analysis: Calcd for C₃₂ H₅₈ N₂ : C, 81.6; H, 12.4; N, 6.0. Found: C,81.8; H, 12.7; N, 5.8.

EXAMPLE 3 N,N,N',N'-Tetracyclohexyl-2-butene-1,4-diamine

A solution of dicyclohexylamine (20.4 g, 0.11 mol) and 2-butene-1,4-dioldiacetate (9.6 g, 0.056 mol) in THF (100 ml) is treated withtetrakis(triphenylphosphine)palladium (0) (1.0 g, 0.9 mmol) and stirredat room temperature overnight. The reaction mixture is concentrated invacuo to a solid that is redissolved in THF (500 ml) and treated with20% aqueous sodium hydroxide (250 ml). The mixture is stirred for onehour, concentrated, and extracted with ether. The ether extracts aredried and concentrated giving an orange solid which is purified bycrystallization from isopropyl alcohol. The title compound is isolatedas a while solid in a yield of 4.8g (21%): mp 136°-138° C.

Analysis: Calcd for C₂₈ H₅₀ N₂ : C, 81.1; H, 12.2; N, 6.8. Found C,80.8; H, 12.7; N, 6.7

EXAMPLE 4 N,N,N',N'-Tetrabenzyl-2-butene-1,4-diamine

A solution of dibenzylamine (13.0 g, 66 mmol) and 2-butene-1,4-dioldiacetate (4.0 g, 33 mmol) in 50 ml of tetrahydrofuran (THF) is treatedwith tetrakis(triphenylphosphine)palladium(0) (1.0 g, 0.9 mmol) andstirred at room temperature overnight. The reaction mixture isconcentrated in vacuo to a solid that is redissolved in THF (100 ml) andtreated with 20% aqueous sodium hydroxide (25 ml). The mixture isstirred for one hour, then concentrated and extrated with diethyl ether.The ether extracts are dried and concentrated to give 6.9 g (47% yield)of the title compound as a white solid melting at 114°-115° C.

Analysis: Calcd for C₃₂ H₃₄ N₂ : C, 86.1; H, 7.7; N, 6.3. Found: C,86.1; H, 7.7; N, 6.2.

EXAMPLE 5 N,N,N',N'-Tetraphenyl-2-butene-1,4-diamine

A vigorously stirred mixture of diphenylamine (150 g, 0.9 mol),1,4-dibromobut-2-ene (104 g, 0.49 mol), potassium iodide (8 g, 0.05mol), tetrabutylammonium bromide (7 g, 0.025 mol), sodium hydroxide (43g, 1.06 mol) and 150 ml of water is warmed to 60° C. for five hours. Themixture is allowed to cool to room temperature. The solids formed arecollected and washed with water. The residue is recrystallized fromethanol to give 69 grams (36% yield) of the title compound as a tansolid melting at 105°-107° C.

Analysis: Calcd for C₂₈ H₂₆ N₂ : C, 86.1; H. 6.7; N, 7.2. Found: C,85.8; H, 6.5; N, 7.2.

EXAMPLE 6 N,N'-Diphenyl-N,N'-di-1-naphthyl-2-butene-1,4-diamine

A mixture of N-phenyl-1-naphthylamine (63 g, 0.29 mol) and1.4-dibromobut-2-ene (12 g, 0.056 mol) is heated to 70° C. for threedays. The resulting reaction mass is allowed to cool and is thenextracted with 3×100 ml of hot hexane. The combined hexane extracts areconcentrated in vacuo to an oil which is chromatographed (silica gel.95/5 cyclohexane/diethyl ether) to give an oil. Said oil is thencrystallized from ether to give 4.8 g (17.5% yield) of the titlecompound as a tan solid melting at 140°-142° C.

EXAMPLE 7 N,N'-Dibenzyl-N,N'-di-α-methylbenzyl-2-butene-1,4-diamine

The procedure of Example 4 is repeated with N-benzyl-α-methylbenzylamineprepared by the method of M. Brook et al., Synth. Comm. 18, 893 (1988).The title compound is obtained in a 20% yield after recrystallizationfrom isopropanol as a white solid melting at 131°-134° C.

Analysis: Calcd for C₃₄ H₃₈ N₂ : C, 86.0; H, 8.1; N, 5.9. Found: C,85.1; H, 8.2; N, 5.7.

EXAMPLE 8 N,N'-Dicyclohexylmethyl-N,N'-dibenzyl-2-butene-1,4-diamine

The general procedure of Example 4 is repeated withN-cyclohexylmethyl-N-benzylamine prepared by the method of S. C. Shim etal., Tetrahedron Letters 31, 105 (1990). After crystallization fromisopropanol, the title compound is obtain in an 82% yield as a whitesolid melting at 92°-93° C.

Analysis: Calcd for C₃₂ H₄₆ N₂ : C, 83.8; H, 10.1; N, 6.1. Found: C,83.9; H, 10.3; N, 6.1.

EXAMPLE 9 N,N'-Dibenzyl-N,N'-di-2-cyanoethyl-2-butene-1,4-diamine

Following the general procedure of Example 4 using3-(benzylamino)propionitrile and after purification of the crude productby chromatography, the title compound is obtained as a clear oil in ayield of 65%.

Analysis: Calcd for C₂₄ H₂₈ N₄ : C, 77.4; H, 7.6; N, 15.1. Found: C,76.9; H, 7.5; N, 15.1.

EXAMPLE 10 N,N'-Di-1-naphthylmethyl-N,N'-dibenzyl-2-butene-1,4-diamine

The general procedure of Example 4 is repeated withN-1-naphthylmethyl-N-benzylamine prepared by the method of Dahn et at.,Helv. Chim. Acta. 37, 565 (1954). After crystallization from 30% ethylacetate in isopropanol, the title compound is obtained in a yield of 35%as a white solid melting at 121°-122° C.

Analysis; Calcd for C₄₀ H₃₈ N₂ : C, 87.9; H, 7.0; N, 5.1. Found: C,87.5; H, 7.0; N, 5.0.

EXAMPLE 11 N,N-Dicyclohexylmethyl-N',N'-dibenzyl-2-butene-1,4-diamine

A solution of dibenzylamine (40 g, 0.2 mol) and 2-butene-1,4-dioldiacetate (105 g, 0.61 mol) dissolved in 150 ml of tetrahydrofuran (THF)is treated with tetrakis(triphenylphosphine)palladium(0) (1.0 g, 0.9mmol) and stirred at room temperature overnight. The reaction mixture isconcentrated in vacuo and the excess 2-butene-1,4-diol diacetate isremoved by bulb-to-bulb distillation at 80°-90° C./1 mm. The residue ispurified by eluting through a short plug of silica gel (1:1 ethylacetate:hexanes). 1-Acetoxy-4-dibenzylamino-2-butene is obtained in ayield of 59.2 g (95%).

A solution of 1-acetoxy-4-dibenzylamino-2-butene (10.1 g, 33 mmol) anddicyclohexylmethylamine (6.8 g, 32 mmol) in 50 ml of THF is treated withtetrakis(triphenylphosphine)palladium (0) (1.0 g, 0.9 mmol) and stirredat room temperature overnight. The reaction mixture is concentrated invacuo to a solid which is redissolved in 100 ml of THF and treated with25 ml of 20% aqueous sodium hydroxide. The mixture is stirred for onehour, concentrated and extracted with diethyl ether. The ether extractsare dried and concentrated to give a solid which is then purified bycrystallization from isopropanol. The title compound is obtained in ayield of 9.7 g (65%) as a white solid melting at 61°-62° C.

Analysis: Calcd for C₃₂ H₄₆ N₂ : C, 83.8; H, 10.1; N, 6.1. Found: C,83.8; H, 10.2; N, 5.9.

EXAMPLE 12 N,N,N',N'-Tetra-p-methoxycarbonylbenzyl-2-butene-1,4-diamine

Di(p-carboxybenzyl)amine (17.2 g, 0.06 mol), prepared according to themethod given in U.S. Pat. No. 3,335,176, is suspended in 300 ml ofmethanol. The suspension is then saturated with hydrogen chloride gaswithout cooling. The resulting mixture is then refluxed for five hours,cooled and finally concentrated to a solid. The solid is suspended inwater, the aqueous suspension is then made basic using ammoniumhydroxide and finally extracted with ethyl acetate. The organic extractsare dried over anhydrous magnesium sulfate and concentrated to givedi(p-methoxycarbonylbenzyl)amine as an oil.

Di(p-methoxycarbonylbenzyl)amine (14.1 g, 0.045 mol) and2-butene-1,4-diol diacetate (3.9 g, 0.023 mol) are dissolved in 150 mlof THF. Tetrakis(triphenylphosphine)palladium (0) (1.0 g, 0.9 mmol) isadded and the resulting solution is stirred for three days at roomtemperature. The solution is concentrated, the residue redissolved inTHF and treated with 20 ml of ammonium hydroxide solution, stirred for15 minutes and finally concentrated to a solid which is washed withwater, diethyl ether and dried. The title compound is obtained in a 72%yield as a white solid melting at 161°-163° C.

EXAMPLE 13 N,N,N',N'-Tetra-p-methoxybenzyl-2-butene-1,4-diamine

Following the general procedure of Example 4 by replacing dibenzylaminewith an equivalent amount of di(p-methoxybenzyl)amine, prepared by themethod of Tanaka et al., Chem. Pharm. Bull, 15, 774 (1067), the titlecompound is afforded in a 33% yield as a white solid melting at128°-130° C.

EXAMPLE 14 N,N-Diphenyl-N',N'-dibenzyl-2-butene-1,4-diamine

Following the general procedure of Example 11 by replacing1-acetoxy-4-dibenzylamino-2-butene with1-acetoxy-4-diphenylamino-2-butene and replacing dicyclohexylmethylaminewith dibenzylamine, the title compound is obtained as a white solid.

EXAMPLE 15 Process Stabilization of Dynamically CrosslinkedPolypropylene/Nitrile Rubber

A Brabender cavity heated to 190° C. is charged with 55 g of adynamically crosslinked polypropylene/nitrile rubber resin (GEOLAST,Monsanto). The resin is stirred under nitrogen for three minutes, 4% byweight of the stabilizer test compound is added and mixed under nitrogenfor an additional seven minutes. The sample is removed, flattened in acold press, and is subjected to the following procedure:

Compression Molding

Plaques [60 mil and 4"×4" (1.524 mm and 10.16 cm×10.16 cm)] are preparedby loading 18-20 g of said rubber per plaque. The temperature of thecompression molding press platens is adjusted to 200° C. The resin ispreheated to allow it to flow. The resin is compression molded at lowpressure [2000 psi (140 Kg/cm²)] for four minutes and at high pressure[50,000 psi (3500 Kg/cm²)] for four minutes.

Sample Preparation and Oven Aging

The samples are cut on a Naef press using Die C whose dimensions aredescribed in ASTM D412. The cut samples are mounted in replicates andoven aged at 135° C. for seven days before tensile testing for %retention of elongation according to ASTM D412. A greater % retention ofelongation indicates a more effective stabilizer.

    ______________________________________                                        Test Compound*                                                                              % Retention of Elongation                                       of Example    After 7 Days at 135° C.                                  ______________________________________                                        Blank         0                                                               AOI           10                                                              Example 1     50                                                              Example 2     52                                                              Example 4     40                                                              Example 5     55                                                              Example 6     52                                                              Example 8     68                                                              Example 10    90                                                              Example 11    64                                                              Example 12    54                                                              Example 14    77                                                              ______________________________________                                         *AOI is the oligomeric condensation product of diphenylamine and acetone.

The instant compounds are clearly more effective as stabilizers than theprior art stabilizer in this crosslinked polypropylene/nitrile rubber.

EXAMPLE 16 Stabilization of Gasoline Engine Oils

The antioxidant effectiveness of the instant compounds in engine oils ismeasured by the Thin-Film Oxygen Uptake Test (TFOUT) designated by theASTM D4742 method. A 1.5 gram test sample of 10W30 engine oil,formulated to meet the SD/CC quality level and containing 0.5% by weightof the test compound, is placed in the test apparatus. The test is thencarried out according to the standard procedure and the oxidationinduction time, in minutes, is ascertained. A longer induction timeindicates a more effective antioxidant stabilizer.

    ______________________________________                                        Test Compound of                                                                             Oxidation Induction Time (minutes)                             ______________________________________                                        Base Oil (no stabilizer)                                                                     113                                                            Example 4      138                                                            ______________________________________                                    

The instant compound provides effective antioxidant protection to thebase oil.

What is claimed is:
 1. A composition stabilized against the deleteriouseffects of heat or oxygen which comprises(a) a synthetic polymer, and(b) an effective stabilizing mount of a compound of formula I, II or III##STR5## wherein R₁, R₂, R₃ and R₄ are independently a linear orbranched alkyl of 8 to 30 carbon atoms; alkyl of 1 to 20 carbon atomssubstituted with cycloalkyl of 5 to 12 carbon atoms; or alkyl of 1 to 20carbon atoms terminated with --OR₅, --NR₆ R₇, --SR₈, --COOR₉ or --CONR₁₀R₁₁, where R₅, R₆, R₇, R₈ and R₉ are independently alkyl of 1 to 20carbon atoms or alkenyl of 3 to 18 carbon atoms, and R₁₀ and R₁₁ areindependently hydrogen or the same meaning as R₅ ; or alkyl of 3 to 18carbon atoms interrupted by one or more --O--, --S--, --SO--, --SO₂ --,--CO--, --COO--, --OCO--, --CONR₁₂ --, --NR₁₂ CO-- or --NR₁₃ -- whereR₁₂ and R₁₃ have the same meaning as R₁₀ ; or R₁, R₂, R₃ and R₄ areindependently cycloalkyl of 5 to 12 carbon atoms; or alkenyl of 3 to 20carbon atoms;E₁ is aralkyl of 7 to 15 carbon atoms or said aralkylsubstituted on the aryl ring by one to three groups selected from alkylof 1 to 12 carbon atoms, --CN, --NO₂, halogen, --OR₅, --NR₆ R₇, --SR₈,--COOR₉ or --CONR₁₀ R₁₁, where R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are asdefined above, E₂, E₃ and E₄ are independently a linear or branchedalkyl of 1 to 30 carbon atoms; alkyl of 1 to 20 carbon atoms substitutedwith cycloalkyl of 5 to 12 carbon atoms; or alkyl of 1 to 20 carbonatoms terminated with --CN, --OR₅, --NR₆ R₇, --SR₈, --COOR₉ or --CONR₁₀R₁₁, where R₅, R₆, R₇, R₈ and R₉ are independently alkyl of 1 to 20carbon atoms or alkenyl of 3 to 18 carbon atoms, and R₁₀ and R₁₁ areindependently hydrogen or the same meaning as R₅ ; or alkyl of 3 to 18carbon atoms interrupted by one or more --O--, --S--, --SO--, --SO₂ --,--CO--, --COO--, --OCO--, --CONR₁₂ --, -- NR₁₂ CO-- or --NR₁₃ -- whereR₁₂ and R₁₃ have the same meaning as R₁₀ ; or E₂, E₃ and E₄ areindependently cycloalkyl of 5 to 12 carbon atoms, alkenyl of 3 to 20carbon atoms, aralkyl of 7 to 15 carbon atoms or said aralkylsubstituted on the aryl ring by one to three groups selected from alkylof 1 to 12 carbon atoms, --CN; --NO₂, halogen, --OR₅, --NR₆ R₇, --SR₈,--COOR₉ or --CONR₁₀ R₁₁, where R₅, R₆, R₇, R₈, R₉, R₁₀ and R₁₁ are asdefined above, or aryl of 6 to 10 carbon atoms or said aryl substitutedby one to three substituents selected from the group consisting of alkylof 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms and aralkylof 7 to 15 carbon atoms, and T₁, T₂, T₃ and T₄ are independently phenylor 1-naphthyl.
 2. A composition according to claim 1 wherein thesynthetic polymer is a polyolefin or an elastomer.
 3. A compositionaccording to claim 2 wherein the polyolefin is polypropylene.
 4. Acomposition according to claim 2 wherein the elastomer is crosslinkedpolypropylene/nitrile rubber.
 5. A composition according to claim 1wherein the compound of component (b) is of formula I where R₁, R₂, R₃and R₄ are independently cycloalkyl of 5 or 6 carbon atoms, a linear orbranched alkyl of 8 to 20 carbon atoms or alkyl of 1 to 4 carbon atomssubstituted with cycloalkyl of 5 or 6 carbon atoms.
 6. A compositionaccording to claim 5 wherein R₁, R₂, R₃ and R₄ are the same and arealkyl of 8 to 18 carbon atoms, cyclohexyl or cyclohexylmethyl.
 7. Acomposition according to claim 1 wherein the compound of component (b)is of formula II where E₁ is benzyl, benzyl substituted on the phenylring by alkyl of 1 to 8 carbon atoms; α-methylbenzyl or1-naphthylmethyl, and E₂, E₃ and E₄ are independently alkyl of 1 to 20carbon atoms, benzyl, benzyl substituted on the phenyl ring by alkyl of1 to 8 carbon atoms or by methoxycarbonyl; α-methylbenzyl; phenyl,1-naphthyl or said phenyl or said 1-naphthyl substituted by alkyl of 1to 8 carbon atoms; cyclohexylmethyl or 2-cyanoethyl.
 8. A compositionaccording to claim 7 wherein E₃ has the same meaning as E₁ and is benzylor 1-naphthylmethyl; and E₂ and E₄ are alkyl of 1 to 20 carbon atoms,benzyl or 1-naphthylmethyl.
 9. A composition according to claim 1wherein T₁ and T₃ are phenyl, and T₂ and T₄ are phenyl or 1-naphthyl.10. A composition according to claim 9 wherein T₁, T₂, T₃ and T₄ areeach phenyl.
 11. A composition according to claim 1 wherein the compoundof component (b) isN,N,N',N'-tetradecyl-2-butene-1,4-diamine;N,N,N',N'-tetracyclohexylmethyl-2-butene-1,4-diamine;N,N,N',N'-tetracyclohexyl-2-butene-1,4-diamine;N,N,N',N'-tetrabenzyl-2-butene-1,4-diamine;N,N,N',N'-tetraphenyl-2-butene-1,4-diamine;N,N'-diphenyl-N,N'-di-1-naphthyl-2-butene-1,4-diamine;N,N'-dibenzyl-N,N'-di-α-methylbenzyl-2-butene-1,4-diamine;N,N'-dicyclohexylmethyl-N,N'-dibenzyl-2-butene-1,4-diamine;N,N'-dibenzyl-N,N'-di-2-cyanoethyl-2-butene-1,4-diamine;N,N'-di-1-naphthyl-N,N'-dibenzyl-2-butene-1,4-diamine;N,N-dicyclohexylmethyl-N',N'-dibenzyl-2-butene-1,4-diamine;N,N,N',N'-tetra-p-methoxycarbonylbenzyl-2-butene-1,4-diamine;N,N,N',N'-tetra-p-methoxybenzyl-2-butene-1,4-diamine; orN,N-diphenyl-N',N '-dibenzyl-2-butene-1,4-diamine.
 12. A compositionstabilized against the deleterious effects of heat or oxygen whichcomprises(a) lubricant, and (b) an effective stabilizing amount of acompound of formula I, or II ##STR6## wherein R₁, R₂, R₃ and R₄ areindependently a linear or branched alkyl of 8 to 30 carbon atoms; alkylof 1 to 20 carbon atoms substituted with cycloalkyl of 5 to 12 carbonatoms; or alkyl of 1 to 20 carbon atoms terminated with --OR₅, --NR₆ R₇,--SR₈, --COOR₉ or --CONR₁₀ R₁₁, where R₅, R₆, R₇, R₈ and R₉ areindependently alkyl of 1 to 20 carbon atoms or alkenyl of 3 to 18 carbonatoms, and R₁₀ R₁₁ are independently hydrogen or the same meaning as R₅; or alkyl of 3 to 18 carbon atoms interrupted by one or more --O--,--S--, --SO--, --SO₂ --, --CO--, --COO--, --OCO--, --CONR₁₂ --, -- NR₁₂CO-- or --NR₁₃ -- where R₁₂ and R₁₃ have the same meaning as R₁₀ ; orR₁, R₂, R₃ and R₄ are independently cycloalkyl of 5 to 12 carbon atoms;or alkenyl of 3 to 20 carbon atoms;E₁ is aralkyl of 7 to 15 carbon atomsor said aralkyl substituted on the aryl ring by one to three groupsselected from alkyl of 1 to 12 carbon atoms, --CN, --NO₂, halogen,--OR₅, --NR₆ R₇, --SR₈, --COOR₉ or --CONR₁₀ R₁₁, where R₅, R₆, R₇, R₈,R₉, R₁₀ and R₁₁ are as defined above, and E₂, E₃ E₄ are independently alinear or branched alkyl of 1 to 30 carbon atoms; alkyl of 1 to 20carbon atoms substituted with cycloalkyl of 5 to 12 carbon atoms; oralkyl of 1 to 20 carbon atoms terminated with --CN, --OR₅, --NR₆ R₇,--SR₈, --COOR₉ or --CONR₁₀ R₁₁, where R₅, R₆, R₇, R₈ and R₉ areindependently alkyl of 1 to 20 carbon atoms or alkenyl of 3 to 18 carbonatoms, and R₁₀ R₁₁ are independently hydrogen or the same meaning as R₅; or alkyl of 3 to 18 carbon atoms interrupted by one or more --O--,--S--, --SO--, --SO₂ --, --CO--, --COO--, --OCO--, --CONR₁₂ --, --NR₁₂CO-- or --NR₁₃ -- where R₁₂ and R₁₃ have the same meaning as R₁₀ ; orE₂, E₃ and E₄ are independently cycloalkyl of 5 to 12 carbon atoms,alkenyl of 3 to 20 carbon atoms, aralkyl of 7 to 15 carbon atoms or saidaralkyl substituted on the aryl ring by one to three groups selectedfrom alkyl of 1 to 12 carbon atoms, --CN, --NO₂, halogen, --OR₅, --NR₆R₇, --SR₈, --COOR₉ or --CONR₁₀ R₁₁, where R₅, R₆, R₇, R₈, R₉, R₁₀ andR₁₁ are as defined above, or aryl of 6 to 10 carbon atoms or said arylsubstituted by one to three substituents selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12carbon atoms and aralkyl of 7 to 15 carbon atoms.
 13. A compositionaccording to claim 12 wherein the compound of component (b) is offormula I where R₁, R₂, R₃ and R₄ are independently cycloalkyl of 5 or 6carbon atoms, a linear or branched alkyl of 8 to 20 carbon atoms oralkyl of 1 to 4 carbon atoms substituted with cycloalkyl of 5 or 6carbon atoms.
 14. A composition according to claim 13 wherein R₁, R₂, R₃and R₄ are the same and are alkyl of 8 to 18 carbon atoms, cyclohexyl orcyclohexylmethyl.
 15. A composition according to claim 12 wherein thecompound of component (b) is of formula II where E₁ is benzyl, benzylsubstituted on the phenyl ring by alkyl of 1 to 8 carbon atoms;α-methylbenzyl or 1-naphthylmethyl, and E₂, E₃ E₄ are independentlyalkyl of 1 to 20 carbon atoms, benzyl, benzyl substituted on the phenylring by alkyl of 1 to 8 carbon atoms or by methoxycarbonyl;α-methylbenzyl; phenyl, 1-naphthyl or said phenyl or said 1-naphthylsubstituted by alkyl of 1 to 8 carbon atoms; cyclohexylmethyl or2-cyanoethyl.
 16. A composition according to claim 15 wherein E₃ has thesame meaning as E₁ and is benzyl or 1-naphthylmethyl; and E₂ E₄ arealkyl of 1 to 20 carbon atoms, benzyl or 1-naphthylmethyl.
 17. Acomposition according to claim 12 wherein the compound of component (b)isN,N,N',N'-tetradecyl-2-butene-1,4-diamine;N,N,N',N'-tetracyclohexylmethyl-2-butene-1,4-diamine;N,N,N',N'-tetracyclohexyl-2-butene-1,4-diamine;N,N,N',N'-tetrabenzyl-2-butene-1,4-diamine;N,N'-dibenzyl-N,N'-di-α-methylbenzyl-2-butene-1,4-diamine;N,N'-dicyclohexylmethyl-N,N'-dibenzyl-2-butene-1,4-diamine;N,N'-dibenzyl-N,N'-di-2-cyanoethyl-2-butene-1,4-diamine;N,N'-di-1-naphthyl-N,N'-dibenzyl-2-butene-1,4-diamine;N,N-dicyclohexylmethyl-N',N'-dibenzyl-2-butene-1,4-diamine;N,N,N',N'-tetra-p-methoxycarbonylbenzyl-2-butene-1,4-diamine;N,N,N',N'-tetra-p-methoxybenzyl-2-butene-1,4-diamine; orN,N-diphenyl-N',N'-dibenzyl-2-butene-1,4-diamine.